Water-insoluble azo dyestuff containing a 3-(2&#39;-thienoyl-or furoylamino)aniline group

ABSTRACT

WATER INSOLUBLE AZO DYESTUFFS OF THE FORMULA   1-(R1-N(-R2)-),3-(R3-CO-N(-R)-),4-(A-N=N-),X-BENZENE   IN WHICH A REPRESENTS THE RADICAL OF A DIAZO COMPONENT, R REPRESENTS AN ALKYL GROUP HAVING AT MOST 4 CARBON ATOMS, OR A HYDROGEN ATOM, R1 REPRESENTS A HYDROGEN ATOM OR AN ALKYL GROUP THAT MAY BE SUBSTITUTED, R2 REPRESENTS AN ALKYL GROUP THAT MAY BE SUBSTITUTED, R3 REPRESENTS A FIVE-MEMBERED HETEROCYCLIC RADICAL WHICH MUST BE SUBSTITUTED WHEN IT REPRESENTS A FURAN RING, AND X REPRESENTS A HYDROGEN ATOM OR A ALKYL, ALKOXY, ARYLOXY OR ARYLMERCAPTO GROUP ARE USEFUL FOR DYEING POLYESTER FIBERS ORANGE TO VIOLET SHADES OF EXCELLENT FASTNESS TO LIGHT AND SUBLIMATION.

United States Patent Office- 3,751,405 Patented Aug. 7, 1973 ABSTRACT OF THE DISCLOSURE Water insoluble azo dyestuffs of the formula N-COR:

in which A represents the radical of a diazo component, R represents an alkyl group having at most 4 carbon atoms, or a hydrogen atom, R represents a hydrogen atom or an alkyl group that may be substituted, R represents an alkyl group that may be substituted, R represents a five-membered heterocyclic radical which must be substituted when it represents a furan ring, and X represents a hydrogen atom or an alkyl, alkoxy, aryloxy or arylmercapto group are useful for dyeing polyester fibers orange to violet shades of excellent fastness to light and sublimation.

CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of application Ser. No. 757,478, filed Sept. 4, 1968.

The present invention is based on the observation that valuable water-insoluble azo dyestuffs of the formula N-COR:

in which A represents the residue of a diazo component, R represents an alkyl group having not more than 4 carbon atoms or a hydrogen atom, R represents a hydrogen atom or an alkyl group that may be substituted, R represents an alkyl group that may be substituted, R represents a five-membered heterocyclic residue which must be substituted when it represents a furan ring, and X represents a hydrogen atom or an alkyl, alkoxy, aryloxy or arylmercapto group, may be obtained by coupling the diazo compound of an amino with a coupling component of the formula in which X, R, R R and R have the meanings given above.

Dyestutfs that are of special interest are these corresponding to the formula 2 NHCOR:

in which X, A, R R and R have the meanings given above and A represents a substituted benzene residue or a monocyclic or bicyclic heterocyclic residue. Dyestuffs in which X represents a methyl or methoxy group or a hydrogen atom and R represents either a substituted furan ring or a substituted or unsubstituted thiophene ring are especially preferred.

The groups R and R may be alkyl groups containing 1 to 4, preferably 2 to 4 carbon atoms, for example, methyl, ethyl, n-propyl or n-butyl groups, which may be substituted in the usual manner, for example, one or more benzyl or fl-phenylethyl groups, halogenated alkyl groups, for example, fi-chloroethyl, 5,6,,3-trifluoroethyl or p -dichloropropyl groups, fl-cyanoethyl groups, alkoxyalkyl group, for example, B-ethoxyethyl or 6-methoxybutyl groups, hydroxyalkyl groups, for example, B-hydroxyethyl and liq-dihydroxypropyl groups, nitroalkyl groups, for example, fl-nitroethyl groups, carbalkoxy groups, for example, B-carbo-(methoxy-, ethoxy or propoxy)-ethyl groups (in which the terminal alkyl group may carry cyano, carbalkoxy, acyloxy and amino groups) and 13- or 'y-carbo-(methoxyor ethoxy)-propyl groups, acylaminoalkyl groups, for example, ,B-(acetylor formyl)- aminoethyl groups, acyloxyalkyl groups, for example, p-acetoxyethyl and p,' -diacetoxypropyl groups, ;8-(alkylor aryl)-sulphonylalkyl groups, for example, fl-methanesulphonylethyl, fi-ethanesulphonylethyl or B- (para-chlorobenzenesulphonyl)-ethyl groups, alkyl or arylcarbamoyloxyalkyl groups, for example, B-methyl-carbamyloxyethyl and p-phenylcarbamyloxyethyl groups, alkyloxycarbonyloxyalkyl groups, for example, ,B-(methoxy-, ethoxyor isopropyloxy)-carbonyloxyethyl, 'y-acetamidopropyl, fl- (para-nitrophenoxy)-ethyl, fl-(para-hydroxyphenoxy)ethyl, fi-(;3'-acetylethoxycarbonyl)-ethyl, B-[(}3'-cyano, hydroxy-, methoxyor acetoxy-)ethoxycarbonyl]-ethyl, cyanoalkoxyalkyl, fl-carboxyethyl, B-acetylethyl, 'y-aminopropyl, p-diethylaminoethyl, fl-cyanoacetoxyethyl and ,B- benzoylor fi-(para-alkoxyor phenoxy-benzoyD-hydroxyethyl groups.

The groups R, and R preferably contain not more than 18 carbon atoms. The residues R and R are preferably alkyl groups substituted by hydroxy, alkoxy, cyanoalkoxy, acyloxy or cyano groups.

The residue R is a heterocyclic ring which must be substituted when it contains an oxygen atom as hetero atom. Suitable substituents are, for example, aryl groups, alkyl groups containing not more than 4 carbon atoms, chlorine atoms or carboxyl groups, or an alkylene chain bound on both sides to the hetero ring.

The diazo components preferably correspond to the formula WQNH.

The following amines are given as exampls of diazo components:

1-amino-4-chlorobenzene, 1-amino-4-bromobenzene, 1-amino-4-methylbenzene, 1-amino-4-nitrobenzene, 1-amino-4-cyanobenzene, l-amino-2,5-dicyanobenzene, 1-amino-4-methylsulphonylbenzene, 1-amino-4-carbomethoxybenzene, 1-amino-2,4-dichlorobenzene, l-amino-2,4-dibromobenzene, 1-amino-2-methyl-4-chlorobenzene, 1-amino-Z-trifiuoromethyl-4-chlorobenzene, 1-amino-Z-cyano-4-chlorobenzene, 1-amino-2-carbomethoxy-4-chlorobenzene, 1-amino-2-carbomethoxy-4-nitrobenzene, l-amino-2-chloro-4-cyanobenzene, 1-amino-2-chloro-4-nitrobenzene, 1-amino-2-phenoxy-4-nitrobenzene, 1-amino-2-chloro-4-carbethoxybenzene, 1-amino-2-chloro-4-methylsulphonylbenzene, l-amino-Z-methylsulphonyl-4-chlorobenzene, 1-amino-2-methylsulphonyl-4-nitrobenzene, 1-amino-2,4-dinitrobenzene, 1amino-2,4-dicyanobenzene, 1-amino-2-cyanomethylsulphonylbenzene, 1-amino-2,6-diohloro-4-cyanobenzene, l-amino-Z,6-dichloro-4-nitrobenzene, 1-arnin0-2,4-dicyan0 6-chl0robenzene, 1-amino-2,4-dicyano-6-chlorobenzene, 1-amino-2,5,6-trinitrobenzene, 1-amino-2,4-dinitro-6-chlorobenzene and especially 1-amino-Z-cyano-4-nitrobenzene, 4-aminoazobenzene, 4-amino-3-nitro-1,1'-azobenzene, 4-amino-3-nitro-4'-chloro-1,l'-azobenzene, 4-amino-3-nitro-2-chloro-1,1'-azobenzene, 4-amin0-3-nitr0-2'-meth0xy-l,1-az0benzene and 4-amino-3-nitro-4-methyl-1,1'-azobenzene.

The following are given as examples of heterocyclic diazo components:

2-aminothiazole,

2-amino-5-nitrothiazole, Z-amino-S-cyanothiazole, 2-arnino-4-methyl-5-nitrothiazole, 2-amino-4-methylthiazole, 2amino-4-phenylthiazole,

Z-amino- (4'- chloro -phenylthiazole, Z-amino- (4'-nitro -phenylthiazole, 2-amino-6-chlorobenzthiazole, 2-amino-6-cyanobenzthiazole, 2-amino-6-nitrobenzthiazole, 2-amino-l,3,4-thiadiazole, 2-amino-1,3,5-thiadiazole, 3-methylmercapto-5-amino-1,2,4-thiadiazole and 3 -methylsulphonyl--amino- 1,2,4-thiadiazole.

The coupling components preferably correspond to the formula NHCOR:

in which X represents a hydrogen atom or an alkyl or alkoxy group, R represents a five-membered heterocyclic residue, for example, an aromatic residue, for example, a furan or thiophene residue or a saturated residue, for example, a tetrahydrofuran or tetrahydrothiophene residue and R represents an alkyl, phenyl or heterocyclic residue,

The following coupling components are given as examples:

N,N-diethyl-3 (2'-thienoylamino) -aniline,

N,N-dicyanoethyl -3- 2'-thienoylamino -aniline,

N,N-diacetoxyethyl -3- 2-thienoylarnino) -aniline,

N,N-di- (acetoxyethyl -3- (5 '-carbomethoxy-2'-thienoylamino) -aniline,

N,N-di(acetoxyethy1) -3- (5'-para-nitrophenyl-2'-furoylamino) -aniline,

N,N-di- (acetoxyethyl) -3 (2'-tetrahydrofuroylamino aniline,

N,N-di- (acetoxyethyl) -3- (2'-tetrahydrothienoylamino) aniline,

N-ethyl-N-acetoxyethyl-3- 2'-thienoylarnino -aniline,

N-cyanoethyl-N-acetoxyethyl-3 (2'-thienoylamino aniline,

N- cyanoethyl-N-benzoyloxyethyl-3- (2'-thienoylamino aniline,

N-ethyl-N-cyanoetl1yl-3 2'-thienoyl amino) -aniline,

N,-N-di- (acetoxyethyl -3- 2-thien0ylamino -6-methoxyaniline and N,N-di- (acetoxyethyl -3- 2-tetrahydrofuroylamino) -6- ethoxy aniline.

The residues represented by the symbol R in the coupling components may also be derived from sulpholanecarboxylic acids of the formula CH CH COOH which may carry further substituents bound to the sulpholane ring, or they may be derived from pyrrole-2- carboxylic acid.

The single coupling component may also be replaced by a mixture of different coupling components. In many cases, the afiinity and building-up properties of the dyestuff mixtures so obtained are better than those of the unitary dyestuffs.

Diazotization of the above-mentioned diazo components may be carried out by methods known per se, for example, with the aid of a mineral acid, especially hydrochloric acid, and sodium nitrite, or, for example, with a, solution of nitrosyl-sulphuric acid in concentrated sulphuric acid.

Coupling may also be carried out by a method known per se, for example, in a neutral to acid medium, if necessary, in the presence of sodium acetate or a similar buffer which influences the rate of coupling, or a catalyst, for example, pyridine or a salt thereof.

After coupling, the dyestuffs formed can easily be separated from the coupling mixture, for example, by filtration, because they are substantially insoluble in water.

The dyestuifs of the present invention are eminently suitable for dyeing and printing materials, especially fibres and fabrics, made, for example, from cellulose triacetate, polyacrylonitrile and polyamides, but especially from aromatic polyesters. They produce on these materials strong dyeings possessing excellent properties of fastness, especially excellent fastness to light, sublimation and rubbing. The dyeings may also be subjected to permanent press processing, for example, the Koratron process. Dyeing produced with the new dyestuffs which have been thus treated display excellent fastness to wet treatments and heat.

For dyeing, the new dyestuifs are advantageously used in a state of fine division, and dyeing is carried out in the presence of a dispersing agent, for example, soap, sulphite cellulose waste liquor or a synthetic detergent, or a combination of different wetting and dispersing agents. Prior to dyeing, it is generally advantageous to convert the dyestuff into a dyeing preparation which contains a dispersing agent and the dyestufl in a form Such that a fine dispersion is obtained when the preparation is diluted with water. Such dyestuif preparations may be obtained in a known manner, for example, by reprecipitating the dyestuif from sulphuric acid and grinding the suspension so obtained with sulphite cellulose Waste liquor. If necessary, they may also be obtained by grinding the dyestuif in a highly efficient grinding device in the dry or wet state in the presence or absence of a dispersing agent.

To obtain stronger dyeings on polyethylene terephthalate fibres it is generally advantageous to add a swelling agent to the dyebath, or more especially to carry out the dyeing process under superatmospheric pressure at a temperature above 100 C., for example, at 120 C. Suitable swelling agents are aromatic carboxylic acids for example, benzoic acid and salicylic acid; phenols, for example, orthoor para-hydroxydiphenyl; aromatic halogen compounds, for example, chlorobenzene, ortho-dichlorobenzene and trichlorobenzene; and phenylmethylcarbinol or diphenyl. When carrying out the dyeing process under super-atmospheric pressure it is generally advantageous to render the dyebath slightly acidic, for example, by the addition of a weak acid, for example, acetic acid.

By virtue of their fastness to alkali, the new dyestuffs are also specially suitable for application by the socalled thermofixation process in which the material to be dyed is impregnated at a temperature not exceeding 60 C. with an aqueous dispersion of the dyestuff which advantageously contains 1 to 50% of urea and a thickening agent, especially sodium alginate, and then squeezed in the usual manner. The impregnated material is advantageously squeezed so as to retain 50 to 100% of its dry weight of dye-liquor.

To fix the dyestuff, the material so impregnated is heated to a temperature above 100 C., for example, to a. temperature within the range of from 180 to 220 C., advantageously after drying, for example, in a current of warm air.

The aforementioned thermofixation process is especially suitable for the dyeing of union fabrics made from polyester fibres and cellulosic fibres, especially cotton. In this case, in addition to the dyestuffs of the invention, the padding liquor contains dyestuffs suitable for dyeing cotton, especially vat dyestuffs, or reactive dyestulfs, that is to say, dyestuffs capable of being fixed on the cellulosic fibre with formation of a chemical bond, for example, dyestuffs which contain a chlorotriazine or chlorodiazine residue. In the latter case, it is generally advantageous to add an agent capable of binding acid to the padding liquor, for example, an alkali metal carbonate, an alkali metal phosphate, an alkali metal borate or an alkali metal perborate, or mixtures thereof. When using vat dyestuffs, the padded fabric must be treated after the heat treatment with an aqueous alkaline solution of one of the reducing agents commonly used in vat dyeing.

By virtue of the fact that the dyestuffs of the invention reserve well on wool, they are eminently suitable for dyeing union fabrics made from polyester fibre and wool.

The dyeings obtained are advantageously subjected to an after-treatment, for example, by heating with an aqueous solution of an non-ionic detergent.

The dyestuffs may also be applied by printing processes. In this method of application a printing paste is used which contains, for example, in addition to the usual printing adjuvants, for example, thickening and wetting agents, the finely divided dyestuff, if necessary, in admixture with one of the above-mentioned cotton dyestuiis, if necessary, together with urea and/or an agent capable of binding acid.

The following examples illustrates the invention. Unless otherwise stated, the parts and percentages are by weight.

Example 1 0.7 part of sodium nitrite is introduced into 15 parts of sulphuric acid and the batch is stirred. 1.63 parts of 2- cyano-4-nitroaniline are then added at a temperature of 20 to 25 C., the whole is stirred for one hour, discharged on to parts of ice and the excess of nitrite is destroyed with sulphamic acid.

A solution of 3.9 parts of N-bis-acetoxyethyl-S-thienoylaminoaniline in 25 parts by volume of dimethylformamide is added dropwise to the solution so obtained at a temperature not exceeding 10 C., the batch is stirred for three hours and then neutralized with 30% NaOH. The dyestuif is then isolated by filtration and dried. It dyes polyester a violet shade.

Example 2 1.73 parts of 2-chloro-4-nitroaniline are mixed with 20 parts of water and 3 parts by volume of concentrated hydrochloric acid, the batch is cooled to 0 C. and then diazotization is elfected with 6 parts by volume of 2 N- sodium nitrite solution. The batch is stirred for one hour, filtered, and the excess of nitrite is destroyed with sulphamic acid.

A solution of 3.9 parts of N bis-acetoxyethyl-3-thienoylaminoaniline in 25 parts by volume of dimethylformamide is added dropwise to the solution so obtained at a temperature of 0 to 10 C., the batch is stirred for 3 hours and is then neutralized with 30% sodium hydroxide solution. The dyestuif of the formula NHG O u is isolated by filtration and dried. It dyes polyester fibres a bluish red shade possessing excellent fastness to light and sublimation.

The following table lists components for further dyestuffs. The dyestuffs may be obtained by coupling the diazo compounds of the anilines listed in Column I with the coupling components listed in Column H. The shades obtained on polyester fibres are indicated in Column III.

I II III 1 CN 0 Violet:

O-mmmo d om): OzN NH:

I O S 0 NH( 2C CP O CH; lie-i511 2 01 Same as abov BllllSh-l'ed;

OaN NH:

I II III 25 2-amino-5-pheny1-1,3,4-thiadiazo1e Red.

26 4-nitro-3-metl1yl-5-amino-isothiazolo 02H: Bluish red.

NH-C O-fi (J-C 0-0-0211;

HC-GH 27 2-amino-6-cyanobenzathiazol0 Violet.

28 2-amin0-4,6-dinitrobenzothiazo1e. Bluish red.

S NH-C 0l (|3H HC1H 29 2-amino-4-pheny1-1,3,5-thiazo1e Same as above. Red. 30 1-phenyl-3-methyl-5-amino-pym' d0 Yellowish orange.

31 3-amino-5-chloroimidazole C2H4-O-C O-NH-CzH Red.

S NHC OC C H 32.. B-amino-pyridine 02H; Yellow.

\CZHPOH 8 NBC O-C CC O-O OH;

HC- H 33. Z-amino-B-nitro-5-acety1-thiophene /CH Blue: v

CaH4-O-CzHa 34.. 2-am1no-5-nitrobenzoisothiazo1e CH; Do:

85""; 2-aminm5-nitrothiazo1m. /C2HCH2-CN Violet.-

OHzCHz-CN 13 PREPARATION OF THE COUPLING COMPONENTS (I) N-bis(acetoxyethyl)-3-(2'-thienoylamino)-aniline (a) N-bis-acetoxyethyl 3 nitroaniline.--226 parts of N-bis-fi-hydroxyethyl 3 nitroaniline, obtainable according to the process described in Swiss patent specification No. 171,721, together with 250 parts of acetic anhydride, are heated for 3 hours at 130 C., the glacial acetic acid is removed in vacuo, and the residue is distilled in a high vacuum. The product of the formula O IEhOCCHs NO;

is obtained.

Calculated (percent): C, 54.19; H, 5.85; N, 9.03. Found (percent): C, 54.25; H, 5.78; N, 9.05.

(b) N bis-fl-acetoxyethyl-3-aminoaniline.-620 parts of N-bis-fi-acetoxyethyl-S-nitroaniline are hydrogenated in 2,000 parts of absolute alcohol in the presence of Pd/ carbon, the solvent is removed in vacuo, and the residue is distilled in a high vacuum. The product of the formula /C 11 O-Hl-CH: N

QNQMECHJ.

-rtJn is obtained by replacing the 15.5 parts of thiophene-2- carboxylic acid chloride in Example II with 27 parts of 5-(para-nitrophenyl)-furan-2-carboxylic acid chloride.

(IV) N-bis-(acetoxyethyl)-3-(2'-furoylamino)-aniline 14 parts of furan-Z-carboxylic acid chloride are used instead of 15.5 parts of thiophene-Z-carboxylic acid chloride.

(V) N-bis-(acetoxyethyl)-3-(2'-tetrahydrofuroylamino)-aniline 14.5 parts of tetrahydrofuran-Z-carboxylic acid ch1oride are used instead of 15.5 parts of thiophene-Z-carboxylic acid chloride.

The other coupling components may be obtained in an analogous manner.

Dyeing procedure: 1 part of the dyestuif obtained in the manner described in Example 1 is ground wet with 2 parts of a 50% aqueous solution of the sodium salt of l,1-dinaphthylmethane 2,2 disulphonic acid and the batch is dried.

The dyestufi preparation so obtained is mixed with 40 parts of a 10% aqueous solution of the sodium salt of N-benzyl 'y heptadecylbenzimidazole disulphonic acid, and then 4 parts of a 40% acetic acid solution are added. A dyebath of 4,000 parts is prepared therefrom by dilution with water.

parts of cleaned polyester fibre material are entered into this dyebath at 50 C., the temperature is raised to to C. within half an hour and dyeing is carried out for one hour at that temperature in a closed vessel. The material is then rinsed well. A strong, violet dyeing possessing excellent fastness to light and sublimation is obtained.

We claim:

1. A water-insoluble azo dyestuff of the formula N-COR:

in which A represents a diazo component derived from a member selected from the group consisting of (1) unsubstituted thiazole, benzothiazole, isothiazole, benzoisothiazole, 1,3,4-thiadiazole, 1,3,5-thiadiazole, pyrazole, indazole, pyridine or thiophene and (2) said moieties substituted by a member selected from the group consisting of nitro, cyano, halo, methyl, phenyl, methylmercapto, methylsulfonyl, alkoxy having up to 2 carbon atoms or acetyl, R is hydrogen or alkyl having up to 4 carbon atoms, R and R each represents hydrogen, unsubstituted or substituted alkyl containing up to 4 carbon atoms wherein any substituent is selected from the group consisting of cyano, C alkoxy, C carbalkoxy, C alkanoylamino, alkanoyloxy having up to 2 carbon atoms, C alkyloxycarbonyloxy, C alkyl carbamyloxy, fiphenyl-carbamyloxy, ,B-phenoxy, fi-diethylamino, p-cyanoethoxy, p-benzoyloxy, phenyl and only one of R or R being hydrogen at any one time; R represents thienyl, tetrahydrofuryl, tetrahydrothienyl and substituted furyl or thienyl, wherein any substituent is selected from the group consisting of alkyl of up to 4 carbon atoms, chloro, carboxy, carbo-C -C alkoxy, paranitrophenyl and parachlorophenyl, and X is hydrogen, methoxy, ethoxy or methyl.

2. A water-insoluble monazo dyestuif as claimed in claim 1 of the formula l NHCOR;

.in which X, A, R R and R have the meanings given to them in claim 1.

3. A water-insoluble monoazo dyestufi as claimed in claim 1 of the formula 16 4. A water-insoluble monoazo dyestufi as claimed in References Cited clam 3 the fmmnla UNITED STATES PATENTS 2,144,219 1/1939 13126111111161 260-152 2,392,181 1/1946 Parker et al. 260152 O N=NGN(CZH" O*OOCHQZ 5 2,644,753 7/1953 Gaspar et a1. 260- 152 X H5020 S 1 2,683,708 7/1954 Dickey at al 260158 2,683,709 7/1954 Dickey et a1. 260-158 HO OH 3,117,956 1/1964 Lange et a1 260152 10 3,177,198 4/1965 Weis et a1 260-152 5. A monoazo dyestufi as clalmed 1n clalm 2 of the 3,336 236 3 19 7 Sartori 26Q 158 formula CH3 NO, FLOYD D. HIGEL, Primary Examiner C H 11 ILNZN 15 US. Cl. X.R.

s 347.3 NHCOC/ \C--COOC2H5 Patent No. I 3;,7513405 Dated August 7,

Inventorfs) ANGLIICER ET AL It is certified that: error appears in the above-identified patexit and that said Letters Patent are hereby corrected as shown below:

Column 15, claim line 2, delete "claim 3" and substitute claim 2 Signed and sealed this 20th day ofl November 1973.

(SEAL) -& Attest:

EDWARD PLFLETCHERJR. RENE D. TEGI'MEYER Attesting Officer Acting Commissioner of Patents FORM PO-105O (IO-69 I USCOMM'DC 60376-P59.

n u s uovumzm PRINTINC org- 1; H6! \be' an 

